Reaction products of cyclic-substituted naphtholactams and arylamines



United States Patent Oflice 3,391,148 Patented July 2, 1968 16 Claims.61. 260-288) ABSTRACT OF THE DISCLOSURE Novel azo dyestuffs usefulparticularly in the dyeing and printing of acrylonitrile containingfibers are prepared from cyclic substituted naphtholactams andarylamines and have the general formula:

r- A N:C--Ar-N R and R are lower alkyl, substituted lower alkyl,monocyclic aryl, aralkyl and if taken together are or -CH -CH NH-CH CHAr is a monocyclic or bicyclic aromatic ring; X is an anion used forsalt formation of basic dyestuffs; K is hydrogen, chlorine, bromine,lower alkyl, lower alkoxy, amino or nitrile; and n is l or 2; thedyestuif being free of sulfonic acid, carboxylic acid or disulfimidegroups.

The present invention relates to novel dyestuffs; more particularly itrelates to dyestuffs of the formula in this formula A stands for theresidual members of a 5- or fi-mernbered ring containing nitrogen and Aand the naphthalene ring may exhibit non-ionic substituents, Ar denotesan aromatic radical, and R and R represent alkyl, cycloalkyl, aryl oraralkyl radicals, where the alkyl radicals may also conjointly form theconstituent of a saturated heterocyclic ring system and Ar and R as Wellas R may exhibit non-ionic substituents; the dyestuffs are free ofsulfonic acid, carboxylic acid and disulfimide groups; X stands for theresidue of an anion usual in basic dyestuffs, e.g. Cl, Br, the acetate,hydrogen sulfate, phosphate or sulfate radical.

The novel dyestuffs are obtained when compounds of the general formulaDNC=O A l kQ/i (11) wherein A has the above identified meaning andwherein A and the naphthalene ring may exhibit non-ionic substituents,are heated with amines of the general formula ArN E; (III) wherein Ar aswell as R and R have the above identified meaning and wherein thoseradicals as well as the naphthalene ring may exhibit non-ionicsubstituents, in the presence of condensing agents having a watereliminating activity.

The following are for instance suitable compounds of the general FormulaII: cyclic lactams of the formula wherein Z denotes hydrogen, chlorine,bromine, an acetylamin'o, p-toluene-sulfonylamino, dimethylarnino,methoxy, ethoxy, phenoxy, acetyl, methyl or ethyl group, and the cycliclactams of the formula wherein R denotes hydrogen or a methyl or phenylgroup. These compounds can for instance be obtained by reactingcompounds of the formula wherein A has the above specified significanceand A and the naphthalene ring may contain non-ionising substituents,with phosgene in inert solvents or dilue-nts followed by treatment withFriedel-Crafts catalysts.

Suitable compounds of Formula III are, inter alia, N,N- dimethylaniline,N,N-diethylaniline, N-n.buty1 N fichloro-ethyl-aniline, 2-eth-oxy-N,Ndimethylaniline, 3- methyl-dimethylaniline, N methyl diphenylamine, N-ethyl-diphenylamine, N-me'thyl-4-ethoxy-diphenylamine,N-ethyl-4-ethoxy-diphenylamine, I-dimethylarnino-naphthalene and1-diethylamino-naphthalene.

The following can for instance be considered as condensing agents havinga water-eliminating activity: the halides of the acids of phosphorussuch as phosphorus oxychloride, phosphorus oxybromide, phosphoruspentacloride and phosphorus trichloride, as well as sulphuryl andthionyl chloride and also phosgene, stannic chloride, titaniumtetrachloride, zinc chloride, aluminium chloride, boron trifiuoride andsilicon tetrachloride, or their mixtures.

In order to carry out the process according to the invention, it ispossible to proceed by heating the cyclic lactam (II) with theamine(III) to a temperature between 70 and 150 C. optionally in a diluent,and then adding the condensing agent. It is also possible first to heatthe lactam with the condensing agent and thereafter to add the amine;lower temperatures are frequently satisfactory for this form ofexecution, for instance those from 30 to 100 C. However, it will ingeneral be sutficient to apply the amount of amine in equimolarproportions relative to the lactam, although it may also be possible toemploy an excess, when the excess may be selected to be large enough forthe amine to serve as the solvent. In addition, chloroform,1,2-dichloroethane, 1,l,2,2-te-trachloroethane, nitrobenzene,chlorobenzeneand the isomeric diand trichlorobenzenes are suitable asdiluents, as well as phosphorus oxychloride and thionyl chloride.

Suitable non-ionic substituents which may be present in the naphthalenering and/or in the arylene residue Ar are, for instance, halogen atoms,such as fluorine, chlorine and bromine, lower alkyl and lower alkoxygroups, such as the methyl, ethyl, isopropyl, methoxy and ethoxy groups,nitro and amino groups, acyl radicals and sulphonamide groups as Well asnon-ionic derivatives of carboxyl groups such as carboxylic acid ester,carboxylic acid amide and nitrile groups.

It has to be understood that the type of the anion X usual in basicdyestuffs does not effect the dyeing prop-er- -ties of the noveldyestuffs. From their preparation the dyestuffs will normally exhibitanions like halide anions, in particular Cl and/or Br", or sulfonategroups, such as OSO CH or -OSO C H or p-toluene sulfonate; in general,the nature of the anion depends on the mode of production, purificationand/or precipitation of the dyestuff. The anion can, however, bereplaced by other anions normally encountered in dyestuff salts of basicdyestuffs by methods known as such; for this purpose the dyestuff saltis first converted into the free base by neutralizing it with a basicreagent, such as sodium carbonate, sodium hydroxide and the like, andwhen this base is then converted into the form of the desired salt withthe corresponding organic or inorganic acid by means of this procedure,it is possible to obtain dyestufi salts which contain, for example, [B1benzene sulfonate, phosphate, acetate, chloro zincate, perchlorate,nitrate, sulfate, oxalate, formate, citrate, rnaleinate, tartrate,benzoate, lactate, propionate, butyrate or succinate radicals as theanions.

The novel dyestuffs are particularly suitable for dyeing, printing andspin dyeing of materials which consist wholly or predominantly, ingeneral by more than 85%, of polymerised acrylonitrile or vinylidenecyanide. In this connection it is remarkable that when mixtures of suchmaterials with wool are dyed the animal fibre is hardly coloured. Aparticular advantage of the dyestuifs prepared according to theinvention consists in their high dyeing yield which makes possible theproduction of very deep dyeings and prints. The dyeings and prints haveexcellent fastness properties, particularly towards light, pressing,sublimation and washing, and they are characterised by uniformity of theapplied dyeing and a high lustre. The novel dyestuffs are also suitablefor dyeing and printing on tanned cotton, on cellulose esters such ascellulose acetate and on paper materials, as well as for the productionof inks or of pastes for ball point pens.

4 Except Where otherwise specified the parts stated in the followingexamples, which are given for the purpose of illustrating the invention,are parts by weight.

Example 1 10.5 parts of the cyclic lactam of the formula and 11.4 partsof 4-ethoxy-N-methyl-diphenylamine are heated at 90 to 100 C. for to 24hours with parts of 1,2-dichlorobenzene and to parts of phosphorusoxychloride, whilst stirring. The excess of phosphorus oxychloride isthen decomposed by the dropwise addition of water, the dichlorobenzeneis expelled with steam and the crude dyestuiT which had almostcompletely Separated on cooling of the residual aqueous suspension isrecrystallised from 750 to 1000 parts of wa er. The dyestuff is saltedout from the cooled filtrate by the add-ition of about 50 parts of asaturated solution of sodium chloride. Its composition corresponds tothe formula and it dyes polyacrylonitrile materials strongly bluish Jviolet shades with excellent fastness properties.

The cyclic lactam had been prepared as follows:

parts of 7,8-benzo-quinoline are dissolved in 350 parts by volume ofdioxan and hydrogenated at 70 C. with hydrogen at a pressure ofatmospheres after 12.3 parts of Raney nickel had been added to it.Absorption of hydrogen is complete after 21 hours. The catalyst isfiltered off, dioxan is distilled off and the residue is distilled invacuo. 88.6 parts of 1,2,3,4-tetrahydro-7,8-benzoquinoline of 8.1.l10l23 C./0.2 mm. Hg are obtained.

The compound melts at 41-43 C. after it has been recrystallised fromligroin.

78.0 parts of 1,2,3,4-tetrahydro-7,8-benzo-quinoline are dissolved in280 parts by volume of o-dichlorobenzene and phosgene is passed in at160 C. for 3 /2 hours. Air is then passed through the reaction mixtureat C. for 3 hours. 220 parts by volume of o-dichlorobenzene aredistilled off and the resultant carbamic acid chloride is introducedinto a suspension of 106.8 parts of anhydrous aluminium chloride in 154parts by volume of o-dichlorobenzene heated to 140 C. It is stirred at140 C. for 50 minutes, allowed to cool to 40 C. and the reaction mixtureis added to 300 parts of ice water. The organic phase is separated, theaqueous phase is thoroughly shaken with o-dichlorobenzene and thecombined solutions in o-dichlorobenzene are washed with 10% sodiumcarbonate solution and with water. When the solution has been dried oversodium sulphate, o-dichlorobenzene is distilled off in vacuo and theresidue distilled in a high vacuum. 78.2 parts of a compound of theformula tertiary amines is in each case employed in the place of4-ethoxy-N-methyl-diphenyl-amine during this example, equally valuableand very fast dyestulfs are again obtained when the procedure isotherwise unchanged.

Amine: Colour shade of dyeing on polyacrylonitrileN-methyl-diphenylamine Bluish violet. N-ethyl-diphenylamine Bluishviolet.

N methyl 4 methyl diphenylamine Bluish violet. N methyl 4 methoxydiphenylamine Strongly bluish violet.

Example 2 58 parts of the cyclic lactam of the formula Blue.

I Br

and 46 parts of 4-ethoxy-N-methyl-diphenylamine are heated at 90 to 100C. for 20 hours with 200 parts of 1,2 dichlorobenzene and with 420 partsof phosphorus oxychloride. After the excess of phosphorus oxychloridehas been decomposed by the careful dropwise addition of water, thedichlorobenzene is distilled off in steam. The dyestufi of the formulawhich separates during this operation can be purified byrecrystallisation from water or from dilute acetic acid. It gives a bluedyeing on polyacrylonitrile with very good fastness to light. The cycliclactam employed in this example had been prepared as follows:

20.9 parts of the cyclic lactam described in Example 1 are dissolved in110 parts of chlorobenzene. A mixture of 16 parts of bromine and 25parts of chlorobenzene is allowed to run into this solution at 110 to125 C. The bromination mixture is then stirred at 120 to 125 C. foranother 30 minutes and it is thereafter heated to boiling forapproximately another hour. An aqueous suspension of the bromo-lactam ofthe above stated formula is obtained by distilling oil? thechlorobenzene in steam, and this melts at 162 to 164 C. afterrecrystallisation from acetonitrile.

Example 3 58 parts of the cyclic lactam employed in Example 2 and 30parts of N,N-diethylaniline are heated with 100 parts of1,2-dichlorobenzene and with 150 to 175 parts of phosphorus oxychloride.30 parts of anhydrous aluminium chloride are introduced by portionsbetween 70 and 85 C. Whilst stirring well and the pulpy mixture isstirred at to 95 C. for another 10 to 15 hours. Whilst it is still warmthe mass is then placed into 7000 parts of water at 60 to 70 C., stirredat to C. with 5 to 10 parts of active charcoal for about 10 minutes andfiltered off with suction whilst hot. After it has cooled, the filtrateis treated with parts of sodium chloride, when the dyestuff of theformula separates. The dyestuff is suitable for dyeing and printing onpolyacrylonitrile to give reddish blue shades.

When an equivalent amount of N,N-dimethylaniline is employed in place ofthe diethylaniline, a strongly reddish blue dyestutf with similarcoloristic properties is obtained.

Example 4 24.4 parts of the lactam of the formula /CE2 TH: N?=O CH3 and16.5 parts of N-phenylpiperidine are heated at 90 to 100 C. for 24 hourswith 75 parts of phosphorus oxychloride. The melt is cooled, decomposedwith water and the crude dyestufi filtered off with suction. Thedyestuif can be purified with the addition of charcoal byrecrystallizing from water. It corresponds to the formula and dyespolyacrylnitrile reddish blue.

If using instead of the N-phenylpiperidine the equivalent amount ofN-phenyl-pyrrolidine, N-phenyl-morpholine, N,N-diisopropyl-aniline,N-metl1yl-N-isopropyl-aniline, N,N-di-n-butyl-aniline,N-cyclohexyl-N-methylaniline, N-n-butyl-N-B-chloroethyl-aniline,N-di-fi-chloroethyl-aniline, N-methyl-N-/8-cyanoethyl-aniline,N-ethyl-N-B-methoxyethyl-aniline, N-methyl-N-jS-bromoethyl-aniline or2-ethyl-N,N,-dimethylaniline valuable blue-violet to reddish bluedyestuffs are likewise obtained.

The chlorine containing lactam of this example was produced in thefollowing manner:

parts of the cyclic lactam used in Example 1 are 7 heated at the boilfor one hour with 400 parts of carbon tetrachloride and 70 parts ofsulfuryl chloride. After cooling and filtering off with suction thecrude chlorination product (about 100 parts) is recrystallized frommethanol. It melts at 161 C.

What is claimed is: 1. A dyestutf of the formula:

. R A I=CArN l Rt X wherein A is selected from the group consisting of-CH CH CH C0115 CH3 -Clh( )H -CHzC1l2- and CH2(|JH R and R when takenalone are selected from the group consisting of lower alkyl, halo loweralkyl, monocyclic aryl and aralkyl, and when taken together from thegroup consisting of CH CH CH CH CH and CH CH NHCH CH Ar is selected fromthe group consisting of phenylene, naphthylene, and monosubstitutedphenylene or naiphthylene wherein the substituent is selected from thegroup consisting of hydrogen, lower alkyl, lower alkoxy, chlorine,bromine, fluorine, amino, acyl, sulfonamide, carboxylic acid ester,carboxylic acid amide and nitrile groups; X is an anion used for saltformation of basic dyestuffs; K is selected from the group consisting ofhydrogen, chlorine, bromine, lower alkyl, lower alkoxy, amino andnitrile groups; said dyestuff being free of sulfonic acid, canboxylicacid and disulfimide groups.

2. A dyestuif of the formula:

OH, R r=t- R1 CH k wherein L is selected from the group consisting of H,Br and Cl; B is selected from the group consisting of hydrogen, loweralkyl, lower alkoxy, clorine, bromine, fluorine, nitro, amino, acyl,sulfonamide, carboxylic acid ester, carboxylic acid amide and nitrilegroups; R and R are selected from the group consisting of lower alkyl,halo lower alkyl, monocyclic aryl, aralkyl and, if taken together, are amember selected from the group consisting of and X is an anion used forsalt formation of basic dyest uifs, the dyestuffs being free of sulfonicacid, carboxylic acid and disulfirnide groups.

3. The dyestuff of claim 2 wherein B is lower alkyl.

4. The dyestuif of claim 2 wherein B is lower alkoxy.

5. The dyestuff of the formula 9. The dyestuff of the formula 10. Thedyestuff of the formula C H: N: C -N A I Q 0 C 2H5 11. The dyestutf ofthe formula CH2 C2135 12. The dyestuif of the formula 13. The dyestutfof the formula Cans 9 14. The dyestuif of the formula C II;

15. A dyestuff of the formula:

t=t-@- CHzk wherein L is selected from the class consisting of H, Br andCl, R' is selected from the class consisting of lower alkyl having 1 to2 carbon atoms, chloroethyl and cyanoethyl, and X is an anion used forsalt formation of basic dyestufis, the dyestutf being free of sulfonicacid, carboxylic acid and disulfimide groups.

it? 16. A dyestuff of the formula:

UNITED STATES PATENTS 3,090,782 5/1963 Coerner 260286 X NICHOLAS S.RIZZO, Primary Examiner.

ALEX MAZEL, Examiner.

D. G. DAUS, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,391,148 July 2, 1968 Alfred Brack et a1.

It is certified that error appears in the above identified patent andthat said Letters Patent are hereby corrected as shown below: Column 1,line 13, cancel "azo". Column 2, lines 18 and 19,

cancel "as well as the naphthalene ring". Column 6, lines 8 to 17, theright-hand portion of the formula reading "-M(C H should read N(C HColumn 7, line 53, "clorine" should read chlorine line 63, "thedyestuffs" should read the dyestuff Column 10, lines 1 to 9, theright-hand portion of the formula, at the top of the large closingbracket, "x" should read Signed and sealed this 20th day of January1970.

(SEAL) Attest:

Edward M. Fletcher, Jr. W LLIAM E. SCHUYLER, JR.

Attesting Officer Commissioner of Patents

